WO2023087727A1 - Procédé d'extraction et de précipitation de vanadium à l'aide d'une liqueur de lixiviation gazeuse contenant du vanadium et recyclage de liquide résiduel - Google Patents

Procédé d'extraction et de précipitation de vanadium à l'aide d'une liqueur de lixiviation gazeuse contenant du vanadium et recyclage de liquide résiduel Download PDF

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Publication number
WO2023087727A1
WO2023087727A1 PCT/CN2022/102645 CN2022102645W WO2023087727A1 WO 2023087727 A1 WO2023087727 A1 WO 2023087727A1 CN 2022102645 W CN2022102645 W CN 2022102645W WO 2023087727 A1 WO2023087727 A1 WO 2023087727A1
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Prior art keywords
vanadium
leaching
solution
containing carbonated
residual liquid
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PCT/CN2022/102645
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English (en)
Chinese (zh)
Inventor
付自碧
饶玉忠
伍金树
吴优
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攀钢集团研究院有限公司
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Priority to ZA2022/09075A priority Critical patent/ZA202209075B/en
Publication of WO2023087727A1 publication Critical patent/WO2023087727A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the technical field of vanadium extraction metallurgy, in particular to a method for extracting vanadium by utilizing vanadium-containing carbonated leaching solution and recycling the vanadium-precipitated residual solution.
  • Vanadium slag is the main raw material for producing vanadium oxide, and the traditional industrialization process is sodium roasting-water leaching to extract vanadium.
  • the process of sodium roasting consumes a lot of sodium carbonate, and the process cost is relatively high; the content of sodium oxide in the tailings of vanadium extraction is about 6%, which is difficult to reuse; a large amount of solid waste vanadium chromium reduction filter cake and sodium sulfate will be produced in the water treatment process, which is environmentally friendly There are great hidden dangers.
  • a process idea of vanadium slag calcification roasting-carbonation leaching for vanadium extraction was proposed.
  • the main function of the leaching agent is carbonate, and the available reagents include ammonium carbonate, ammonium bicarbonate, sodium carbonate and sodium bicarbonate.
  • Ammonium carbonate and ammonium bicarbonate are easy to decompose under high temperature leaching conditions, the reagent consumption is large, and the solubility of ammonium metavanadate is relatively small.
  • the carbonation leaching solution studied above can recover vanadium by using ammonium salt vanadium precipitation, and the clinker leaching clinker by the upper layer circulation can realize the recycling of sodium, carbonate, and process water, but the temperature of vanadium precipitation is low, and a special refrigeration system is required; A large number of air bubbles will be generated during the feeding process, which will affect the stability control of the leaching process and equipment utilization efficiency; the leaching slurry contains a high concentration of ammonia, which will affect the operating environment and the recycling rate of ammonium salt during solid-liquid separation.
  • the patent application CN109837384A discloses a vanadium extraction process by sodium roasting, adding ammonium carbonate to the leaching solution to precipitate ammonium metavanadate, and the vanadium precipitation wastewater is deammonized by distillation And condense to obtain dilute ammonia water to realize the recycling of ammonium salt and sodium salt.
  • the purpose of the present invention is to overcome the low temperature of vanadium precipitation in the prior art and the need for a special refrigeration system, the supernatant liquid of vanadium precipitation needs a special deammonization process, the low utilization efficiency of leaching equipment when the supernatant liquid of vanadium precipitation directly leaches clinker, and the leaching process
  • a method for extracting vanadium by using vanadium-containing carbonated leaching solution and recycling the vanadium-precipitated residual solution is provided.
  • the present invention provides a method for utilizing vanadium-containing carbonated leaching solution to extract vanadium and recycle the vanadium-precipitated residual liquid, said method comprising the following steps:
  • the desorbent is a solution containing ammonium bicarbonate and sodium bicarbonate.
  • the vanadium-containing carbonation leaching solution is obtained from vanadium slag through calcification roasting-carbonation leaching and/or from vanadium slag through roasting-carbonation leaching.
  • the vanadium concentration in the vanadium-containing carbonated leaching solution is 1-25 g/L, and the sodium concentration is 5-25 g/L.
  • the concentration of vanadium in the vanadium-containing carbonated leaching solution is 5-25 g/L.
  • the pH value of the vanadium-containing carbonated leaching solution is 7.0-9.5.
  • the specific process of step a includes: flowing the vanadium-containing carbonated leachate through the HCO 3 -type anion exchange resin column from top to bottom, and the vanadium is adsorbed by the resin to obtain a vanadium-rich resin and an ion exchange residue.
  • the concentration of ammonium bicarbonate in the desorbent is 100-160 g/L.
  • the concentration of sodium in the desorbent is 15-25 g/L.
  • the molar ratio of the NH 4 + in the ammonium bicarbonate added to the desorption liquid to the vanadium element in the desorption liquid is 1-1.1:1.
  • the leaching agent for the carbonation leaching is a solution containing sodium carbonate and/or sodium bicarbonate.
  • the ion-exchange resin is used as the carrier to realize the exchange of vanadate and bicarbonate, which avoids the refrigeration process required for ammonium salt vanadium precipitation in the traditional method and the influence of ammonium salt introduction on the sodium salt cycle leaching clinker process.
  • the desorption solution can be directly recycled as a desorption agent to realize the recycling of ammonium salts and save the deammonization process of the supernatant liquid required for the circulation of water and sodium salts in the existing process.
  • the invention provides a method for utilizing the vanadium-containing carbonated leaching solution to extract vanadium and to recycle the vanadium-precipitated residual liquid.
  • the method comprises the following steps:
  • the desorbent is a solution containing ammonium bicarbonate and sodium bicarbonate.
  • the HCO 3 -type anion exchange resin is used to separate vanadium and sodium from the vanadium-containing carbonated leaching solution, the vanadate group has a stronger binding capacity with the resin than HCO 3 - , and is adsorbed by the resin, while HCO 3 - is replaced into the solution,
  • the obtained ion-exchange residual liquid is sodium bicarbonate solution and contains a very small amount of sodium vanadate, which can be returned to the carbonation leaching process as a leaching agent to leach clinker obtained by calcification or blank roasting.
  • the vanadium-containing carbonated leaching solution is obtained from vanadium slag through calcification roasting and carbonation leaching.
  • the leaching agent of the carbonation leaching is a solution containing sodium carbonate and/or sodium bicarbonate.
  • the vanadium slag may come from vanadium-containing slag produced by extracting vanadium from vanadium-containing iron, secondary vanadium-containing resources, low-grade vanadium-containing materials, and the like.
  • the vanadium-containing carbonation leaching solution is obtained from vanadium slag through calcification roasting-carbonation leaching and/or from vanadium slag through roasting-carbonation leaching.
  • the vanadium concentration in the vanadium-containing carbonated leaching solution is 1-25 g/L, and the sodium concentration is 5-25 g/L.
  • the concentration of vanadium in the vanadium-containing carbonated leaching solution is 5-25 g/L.
  • the pH value of the vanadium-containing carbonated leaching solution is 7.0-9.5.
  • the specific process of step a includes: flowing the vanadium-containing carbonated leachate through the HCO 3 -type anion exchange resin column from top to bottom, and the vanadium is adsorbed by the resin to obtain a vanadium-rich resin and an ion exchange residue.
  • the concentration of ammonium bicarbonate in the desorbent is 100-160 g/L. Specifically, it may be 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L or 160g/L.
  • the concentration of sodium in the desorbent is 15-25 g/L. Specifically, it can be 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 22g/L, 23g/L, 24g/L or 25g/L.
  • the molar ratio of the NH 4 + in the ammonium bicarbonate added to the desorption liquid to the vanadium element in the desorption liquid is 1-1.1:1.
  • the vanadium-rich resin obtained in step a is desorbed using a solution containing ammonium bicarbonate and sodium bicarbonate as a desorbent.
  • the vanadate is replaced by the concentration difference between HCO3- and vanadate in the desorption solution.
  • the ion exchange resin can be converted into HCO 3 -type and can be recycled to adsorb vanadium; on the other hand, the vanadium-precipitated residual liquid obtained after vanadium-precipitated desorption liquid can be directly returned to step c to circulate and desorb vanadium-rich resin.
  • adding sodium bicarbonate in the desorbent can prolong the time for desorbing liquid crystallization to separate out ammonium metavanadate, avoiding the formation of ammonium metavanadate precipitation in the desorption process of vanadium-rich resin to block the resin pores; simultaneously control the sodium ion concentration 15 ⁇ 25g/L, the HCO 3 - concentration of the desorbent can be increased as much as possible, which is beneficial to the desorption of the vanadium-rich resin, and at the same time, it can avoid the influence of the subsequent vanadium precipitation effect on the high sodium ion concentration.
  • the vanadium precipitation residual liquid obtained in step d can be returned to step c for use as a desorbent, and the ion exchange residual liquid obtained in step a can be used in the carbonation leaching process, and vanadium is removed from the resin in step c
  • the resin obtained after desorption can continue to be recycled for the adsorption of vanadium, which can reduce the generation of waste water and save the cost of vanadium extraction.
  • the vanadium-containing carbonated leaching solution used in the following examples is from vanadium-containing converter vanadium-containing slag through calcification roasting and carbonation leaching (leaching agent is a mixed solution of sodium carbonate and sodium bicarbonate), the main components and pH value are as shown in the table 1.
  • the concentration of ammonium bicarbonate in the desorbent is 120g/L, and the concentration of sodium bicarbonate is 80g/L.
  • the concentration of ammonium bicarbonate in the desorbent is 120g/L, and the concentration of sodium bicarbonate is 70g/L.
  • the concentration of ammonium bicarbonate in the desorbent is 150g/L, and the concentration of sodium bicarbonate is 80g/L.
  • vanadium precipitation rate (weight of ammonium metavanadate ⁇ vanadium content)/(desorption liquid volume ⁇ vanadium concentration) ⁇ 100%
  • Example 1 Example 2
  • Example 3 Vanadium precipitation rate/% 83.20 79.05 85.25

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne le domaine technique de la métallurgie d'extraction de vanadium et en particulier un procédé d'extraction et de précipitation de vanadium à l'aide d'une liqueur de lixiviation gazeuse contenant du vanadium et de recyclage de liquide résiduel. Le procédé comprend les étapes suivantes consistant à : a, permettre à la liqueur de lixiviation gazeuse contenant du vanadium d'être en contact avec une résine échangeuse d'anions de type HCO3 - pour obtenir une résine riche en vanadium et un liquide résiduel d'échange d'ions ; b, renvoyer le liquide résiduel d'échange d'ions à un procédé de lixiviation par carbonatation afin qu'il soit utilisé ; c, permettre à la résine riche en vanadium d'être en contact avec un désorbant pour obtenir un liquide de désorption ; d, ajouter du bicarbonate d'ammonium dans le liquide de désorption pour la précipitation de vanadium, et filtrer pour obtenir du métavanadate d'ammonium et du liquide résiduel de précipitation de vanadium ; et e, renvoyer le liquide résiduel de précipitation de vanadium à l'étape c afin qu'il soit utilisé ; le désorbant étant une solution contenant du bicarbonate d'ammonium et du bicarbonate de sodium. Selon le procédé, la résine échangeuse d'ions est utilisée comme support pour obtenir l'échange de radicaux de vanadate et de radicaux de bicarbonate, de telle sorte que le processus technologique de recyclage du vanadium à partir de la liqueur de lixiviation gazeuse et de circulation d'un milieu est simplifié ; l'ensemble du processus technologique est réalisé à température normale, et la consommation d'énergie est réduite.
PCT/CN2022/102645 2021-11-19 2022-06-30 Procédé d'extraction et de précipitation de vanadium à l'aide d'une liqueur de lixiviation gazeuse contenant du vanadium et recyclage de liquide résiduel WO2023087727A1 (fr)

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ZA2022/09075A ZA202209075B (en) 2021-11-19 2022-08-12 Method for extracting vanadium from vanadium-containing carbonate leaching solution and recycling raffinate from vanadium precipitation process

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CN202111391734.3 2021-11-19
CN202111391734.3A CN114293033B (zh) 2021-11-19 2021-11-19 利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法

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CN117403055A (zh) * 2023-10-17 2024-01-16 广东诚一环保科技有限公司 一种废渣中稀有金属回收处理的方法

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CN114293033B (zh) * 2021-11-19 2022-11-22 攀钢集团研究院有限公司 利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法

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Publication number Priority date Publication date Assignee Title
CN117403055A (zh) * 2023-10-17 2024-01-16 广东诚一环保科技有限公司 一种废渣中稀有金属回收处理的方法
CN117403055B (zh) * 2023-10-17 2024-06-07 广东诚一环保科技有限公司 一种废渣中稀有金属回收处理的方法

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